This application is a 371 of PCT/EP96/02246, which was filed on May 24, 1996.
The invention relates to novel phenylpyridazinones, to processes for their preparation, to their use as herbicides and to novel intermediates and to processes for their preparation.
It is known that certain substituted phenylpyridazinones such as, for example, the compounds 5-amino-4-chloro-2-phenyl-pyridazin-3-one and 4-bromo-5-methyl-2-phenyl-pyridazin-3-one have herbicidal properties (cf. DE 1105232 and DE 2706700; cf. also DE 1670309, DE 1670315, DE 1695840, DE 2526643, DE 2808193, DE 2821809 and U.S. Pat. No. 5,298,502). However, the herbicidal activity of these compounds is not in all respects satisfactory.
This invention, accordingly, provides the novel substituted phenylpyridazinones of the general formula (I) 
in which
R1 represents halogen,
R2 represents cyano, carbamoyl, thiocarbamoyl, halogen or represents respectively optionally halogen-substituted alkyl, alkoxy or alkylthio,
R3 represents the grouping xe2x80x94A1xe2x80x94A2xe2x80x94A3 
xe2x80x83in which
A1 represents a single bond, represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 where A4 represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylsulphonyl or aryl-sulphonyl,
A1 furthermore represents respectively optionally halogen-substituted alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene,
A2 represents a single bond, represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 where A4 represents hydrogen, hydroxyl, alkyl, alkoxy, aryl, alkylsulphonyl or arylsulphonyl,
A2 furthermore represents respectively optionally halogen-substituted alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene,
A3 represents hydrogen with the proviso that in this case A1 and/or A2 do not represent a single bond,
A3 furthermore represents hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxy, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen,
A3 furthermore represents respectively optionally halogen- or alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl,
A3 furthermore represents respectively optionally halogen-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxy-carbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl, represents respectively optionally halogen-, cyano-, carboxy-, alkyl- and/or alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl,
A3 furthermore represents respectively optionally nitro-, cyano-, carboxy-, halogen-, alkyl-, halogenoalkyl-, alkyloxy-, halogenoalkyloxy- and/or alkoxy-carbonyl-substituted aryl, aryloxy, aralkyl, arylalkoxy, aryloxycarbonyl or arylalkoxycarbonyl,
A3 furthermore represents respectively optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylalkyl, furylalkyl, thienylalkyl, oxazolylalkyl, isoxazolalkyl, thiazolalkyl, pyridinylalkyl, pyrimidinylalkyl, pyrazolylalkoxy, furylalkoxy, perhydropyranylalkoxy or pyridylalkoxy, or
R2 and R3 together represent one of the groupings below xe2x80x94Q1xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94Q3xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94Q3xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94Q1xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94Q3xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94N(R9)xe2x80x94C(R7;R8)xe2x80x94CQ2xe2x80x94, xe2x80x94C(R7)xe2x95x90Nxe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94C(R7,R8)xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94N(R9)xe2x80x94C(R7;R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90Nxe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94C(R7,R8)xe2x80x94N(R9)xe2x80x94, Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94
xe2x80x83where
Q1, Q2 and Q3 are identical or different and each represents oxygen or sulphur,
R7 and R8 are identical or different and each on its own represents hydrogen, halogen or alkyl, or together they represent alkanediyl, and
R9 represents hydrogen, hydroxyl, represents optionally cyano-, halogen-, alkoxy-, alkyl-carbonyl- or alkoxy-carbonyl-substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulphonyl,
R9 furthermore represents respectively optionally halogen-substituted alkenyl or alkinyl,
R9 furthermore represents respectively optionally halogen- or alkyl-substituted cycloalkyl or cycloalkylalkyl, represents respectively optionally halogen-substituted alkoxy or alkenyloxy, or
R9 furthermore represents respectively optionally cyano-, halogen- alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl or arylalkoxy, and
R4, R5 and R6 are identical or different and each represents hydrogen, cyano, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, halogen or represents respectively optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino,
except for the prior art compounds 2-(2,4,5-trichloro-phenyl)-pyridazin-3-one (cf. Liebigs. Ann. Chem. 697 (1966), 42-61) and 4-chloro-5-dimethylamino-2-(4-chloro-2-fluoro-5-propargyloxy-phenyl)-pyridazin-3-one (cf. U.S. Pat No. 5,298,502), which are excluded by disclaimer.
The novel substituted phenylpyridazinones of the general formula (I) are obtained when
(a) halogenoarenes of the general formula (II) 
xe2x80x83in which
R1, R2 and R3 are each as defined above and
X1 represents halogen
are reacted with pyridazinones of the general formula (III) 
xe2x80x83in which
R4, R5 and R6 are each as defined abovexe2x80x94or with acid adducts or alkali metal salts of compounds of the formula (III)xe2x80x94if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or
(b) aryihydrazines of the general formula (IV) 
xe2x80x83in which
R1, R2 and R3 are each as defined above are reacted with xcex2-trihalomethyl-enones of the general formula (V) 
xe2x80x83in which
R4, R5 and R6 are each as defined above and
X2 represents halogen,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or
(c) hydrazonecarboxylic acids of the general formula (VI) 
xe2x80x83in which
R1, R2, R3, R4, R5 and R6 are each as defined above are cyclocondensed, i.e. reacted with a dehydrating agent, or
(d) 2,4-disubstituted phenylpyridazinones of the general formula (Ia) 
xe2x80x83in which
R1, R2, R4, R5 and R6 are each as defined above are nitrated, i.e. reacted with a nitrating agent.
The compounds of the general formula (I) can also be converted into other compounds of the general formula (I) according to the definition above by further customary methods, for example by nucleophilic substitution (for example R3: Fxe2x86x92OH, SH, NH2, OCH3, NHSO2CH3; R5: Clxe2x86x92N(CH3)2) or by further functional group conversions (for example R2: CONH2xe2x86x92CN, CNxe2x86x92CSNH2; R3: NO2xe2x86x92NH2, NH2xe2x86x92F, Cl, Br, CN, NHSO2CH3, SO2Cl)xe2x80x94cf. also the Preparation Examples.
The novel substituted phenylpyridazinones of the general formula (I) have strong herbicidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which
R1 represents fluorine, chlorine or bromine,
R2 represents cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or represents respectively optionally fluorine- and/or chlorine-substituted alkyl, alkoxy or alkylthio having in each case 1 or 2 carbon atoms,
R3 represents the grouping xe2x80x94A1xe2x80x94A2xe2x80x94A3 
xe2x80x83in which
A1 represents a single bond, represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl,
A1 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A2 represents a single bond, represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl,
A2 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A3 represents hydrogen, with the proviso that in this case A1 and/or A2 do not represent a single bond,
A3 furthermore represents hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxy, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, fluorine, chlorine, bromine,
A3 furthermore represents respectively optionally fluorine-, chlorine- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups,
A3 furthermore represents respectively optionally fluorine- or chlorine-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups,
A3 furthermore represents respectively optionally fluorine-, chlorine- cyano-, carboxy-, C1-C4-alkyl- and/or C1-C4-alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups,
A3 furthermore represents respectively optionally nitro-, cyano-, carboxy-, fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkyloxy-, C1-C4-halogenoalkyloxy- and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenyloxycarbonyl or phenyl-C1-C4-alkoxycarbonyl,
A3 furthermore represents respectively optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C1-C4-alkyl, furyl-C1-C4-alkyl, thienyl-C1-C4-alkyl, oxazolyl-C1-C4-alkyl, isoxazol-C1-C4-alkyl, thiazol-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy, furylmethoxy, represents perhydropyranylmethoxy or pyridylmethoxy, or
R2 and R3 together represent one of the groupings below xe2x80x94Q1xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94Q3xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94Q3xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94Q1xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94Q3xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94N(R9)xe2x80x94C(R7;R8)xe2x80x94CQ2xe2x80x94, xe2x80x94C(R7)xe2x95x90Nxe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94C(R7,R8)xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94N(R9)xe2x80x94C(R7;R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90Nxe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94C(R7,R8)xe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94
xe2x80x83where
Q1, Q2 and Q3 are identical or different and each represents oxygen or sulphur,
R7 and R8 are identical or different and each on its own represents hydrogen, fluorine, chlorine, bromine or C1-C4-alkyl, or together they represent C2-C5-alkanediyl, and
R9 represents hydrogen, hydroxyl, represents optionally cyano-, fluorine-, chlorine-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups,
R9 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms,
R9 furthermore represents respectively optionally fluorine-, chlorine-, bromine- or C1-C4-alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 3 atoms in the alkyl group,
R9 furthermore represents respectively optionally fluorine- and/or chlorine-substituted alkoxy or alkenyloxy having in each case up to 6 carbon atoms, or
R9 furthermore represents respectively optionally cyano-, fluorine-, chlorine-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted benzyl or benzyloxy, and
R4, R5 and R6 are identical or different and each represents hydrogen, cyano, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents respectively optionally fluorine- and/or chlorine-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the alkyl groups,
except for the prior art compounds 2-(2,4,5-trichloro-phenyl)-pyridazin-3-one (cf. Liebigs Ann. Chem. 697 (1966), 42-61) and 4-chloro-5-dimethylamino-2-(4-chloro-2-fluoro-5-propargyloxy-phenyl)-pyridazin-3-one (cf. U.S. Pat. No. 5298502), which are excluded by disclaimer.
The invention relates in particular to compounds of the formula (I) in which
R1 represents fluorine or chlorine,
R2 represents cyano, thiocarbamoyl, fluorine, chlorine, bromine, methyl or trifluoromethyl,
R3 represents the grouping xe2x80x94A1xe2x80x94A2xe2x80x94A3 
xe2x80x83in which
A1 represents a single bond, represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl,
A1 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A2 represents a single bond, represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl,
A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A3 represents hydrogen with the proviso that in this case A1 and/or A2 do not represent a single bond,
A3 furthermore represents hydroxyl, amino, cyano, nitro, carboxy, carbamoyl, sulpho, fluorine, chlorine, bromine,
A3 furthermore represents respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl,
A3 furthermore represents respectively optionally fluorine- or chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl,
A3 furthermore represents respectively optionally fluorine-, chlorine-, cyano-, carboxy-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl, or cyclohexylmethoxycarbonyl,
A3 furthermore represents respectively optionally nitro-, cyano-, carboxy-, fluorine-, chlorine-, bromine-, methyl-, ethyl, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl,
A3 furthermore represents (respectively optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy, or
R2 and R3 together represent one of the groupings below xe2x80x94Q1xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94Q3xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94Q3xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94Q1xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94Q3xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94CQ2xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94, xe2x80x94N(R9)xe2x80x94C(R7;R8)xe2x80x94CQ2xe2x80x94, xe2x80x94C(R7)xe2x95x90Nxe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94C(R7,R8)xe2x80x94, xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94Q1xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90C(R7)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94N(R9)xe2x80x94C(R7;R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94, xe2x80x94C(R7)xe2x95x90Nxe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94CQ2-C(R7,R8)xe2x80x94N(R9)xe2x80x94, xe2x80x94Q1xe2x80x94C(R7,R8)xe2x80x94C(R7,R8)xe2x80x94CQ2xe2x80x94N(R9)xe2x80x94
xe2x80x83where
Q1, Q2 and Q3 are identical or different and each represents oxygen or sulphur,
R7 and R8 are identical or different and each on its own represents hydrogen, fluorine, chlorine, bromine or methyl, or together they represent ethane-1,2-diyl (dimethylene), and
R9 represents hydrogen, hydroxyl, represents optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, acetyl- propionyl-, methoxycarbonyl- or ethoxycarbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R9 furthermore represents respectively optionally fluorine-, chlorine- or brominexe2x80x94substituted propenyl, butenyl, propinyl or butinyl,
R9 furthermore represents respectively optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
R9 furthermore represents respectively optionally fluorine- and/or chlorine-substituted methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyloxy, or
R9 furthermore represents respectively optionally cyano, fluorine-, chlorine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted benzyl or benzyloxy, and,
R4, R5 and R6 are identical or different and each represents hydrogen, cyano, thiocarbamoyl, nitro, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, or represents respectively optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, except for the prior art compounds 2-(2,4,5-trichloro-phenyl)-pyridazin-3-one (cf. Liebigs Ann. Chem. 697 (1966), 42-61) and 4-chloro-5-dimethylamino-2-(4-chloro-2-fluoro-5-propargyloxy-phenyl)-pyridazin-3-one (cf. U.S. Pat. No. 5,298,502), which are excluded by disclaimer.
The general or preferred radical definitions listed above are valid also for the end products of the formula (I) and also, correspondingly, for the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. combinations between the preferred ranges mentioned are also possible.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below. 
Ar has for example the meanings listed below:
2,4,5-trichloro-phenyl, 2,4-dichloro-5-fluoro-phenyl, 2-chloro4,5-difluoro-phenyl, 4-chloro-2,5-difluoro-phenyl, 5-chloro-2,4-difluoro-phenyl, 2-fluoro-5-chloro-4-cyano-phenyl, 2,4,5-trifluoro-phenyl, 2,5-dichloro-4-cyano-phenyl, 2-chloro-5-fluoro-4-cyano-phenyl, 2-chloro-4,5-dicyano-phenyl, 2-chloro-4-fluoro-5-cyano-phenyl, 2,5-difluoro-4-cyano-phenyl, 2-chloro-4-cyano-5-methyl-phenyl, 2,4-dichloro-5-methoxy-phenyl, 2,4-dichloro-5-ethoxy-phenyl, 2,4-dichloro-5-n-propoxy-phenyl, 2,4-dichloro-5-i-propoxy-phenyl, 4-chloro-2-fluoro-5-methoxy-phenyl, 4-chloro-2-fluoro-5-ethoxy-phenyl, 4-chloro-2-fluoro-5-n-propoxy-phenyl, 4-chloro-2-fluoro-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-methyl-phenyl, 2,4-dichloro-5-methyl-phenyl, 2-chloro-4-cyano-5-trifluoromethyl-phenyl, 4-fluoro-3-trifluoro-methyl-phenyl, 2-fluoro-4-cyano-5-trifluoromethyl-phenyl, 2-chloro-4-methyl-5-trifluoromethyl-phenyl, 2-chloro-5-fluoro-4-methoxy-phenyl, 2-fluoro-4-methoxy-5-methyl-phenyl, 2,5-difluoro-4-thiocarbamoyl-phenyl, 2-chloro-4-fluoro-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-methoxy-phenyl, 2-fluoro-4-cyano-5-i-propoxy-phenyl, 2-chloro-4-cyano-5-(2-propinyloxy)-phenyl, 2-fluoro-4-cyano-5-(1-methyl-2-propinyloxy)-phenyl, 2-chloro-4-thiocarbamoyl-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-(2-propenyloxy)-phenyl, 2-fluoro4-chloro-5-(2-propenyloxy)-phenyl, 2-chloro-4-cyano-5-methylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-ethyl-sulphonylamino-phenyl, 2-fluoro-4-thiocarbamoyl-5-methylsulphonyl-phenyl, 2-chloro-4-cyano-5-ethylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-cyclopropylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-i-propylsulphonylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-ethylsulphonylamino-phenyl, 2-chloro-4-cyano-5-cyanamino-phenyl, 2-fluoro-4-cyano-5-trifluoromethylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-(2,2-difluoroethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-phenylsulphonylamino-phenyl, 2-fluoro-4-cyano-5-t-butylsulphonylamino-phenyl, 2-chloro-4-cyano-5-methoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonylphenyl, 2-fluoro-4-thiocarbamoyl-5-methoxycarbonyl-phenyl, 2-chloro-4-cyano-5-(N-cyclopropyl-ethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-(1-methyl-2-propinylthio)-phenyl, 2-fluoro-4-cyano-5-methylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-methoxycarbonylmethyl-phenyl, 2-chloro-4-cyano-5-(N-methylethylsulphonylamino)-phenyl, 2-chloro-4-cyano-5-i-propoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-(bis-ethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-(N-methylsulphonyl-ethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-(1-methoxycarbonylethoxy)-phenyl, 2-fluoro-4-cyano-5-cyclo-propyloxy-phenyl, 2-chloro-4-cyano-5-dimethylamino-phenyl, 2-fluoro-4-cyano-5-tetrahydrofurylmethoxy-phenyl, 2-fluoro-4-cyano-5-amino-phenyl, 2-fluoro-4-cyano-5-methylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5-methylsulphonyloxy-phenyl, 2-chloro-4-cyano-5-difluoromethoxy-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonylmethoxy-phenyl, 2-fluoro-4-cyano-5-dimethylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5-cyanomethoxy-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl, 2-fluoro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-5-nitro-phenyl, 2-fluoro-4-cyano-5-diethoxyphosphorylamino-phenyl, 2-fluoro-4-cyano-5-chlorosulphonyl-phenyl, 2-fluoro-4-cyano-5-formylamino-phenyl, 2-chloro-4-cyano-5-ethoxycarbonyloxy-phenyl, 2-fluoro-4-cyano-5-diethoxyphosphorylmethoxy-phenyl, 2-chloro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-5-(N,N-diacetylamino)-phenyl, 2-fluoro-4-cyano-5-acetylamino-phenyl, 2-chloro-4-cyano-5-thiocyanato-phenyl, 2-fluoro-4-cyano-5-diethylaminooxy-phenyl, 2-fluoro-4-cyano-5-tetrahydrofuryloxy-phenyl, 2-fluoro-4-cyano-5-ureido-phenyl, 2-fluoro-4-cyano-5-dimethoxymethyleneamino-phenyl, 2-chloro-4-cyano-5-ethoxymethyleneamino-phenyl, 2-fluoro-4-cyano-5-(2-chloroethoxycarbonyloxy)-phenyl, 2-chloro-4-cyano-5-dimethylaminomethyleneamino-phenyl, 2-chloro-4-cyano-5-(perhydropyran-4-yloxy)-phenyl, 2-fluoro-4-cyano-5-(2-methoxycarbonylethyl)-phenyl, 2-chloro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-s-butoxycarbonyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-carbamoyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-1-methyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(1,2-dibromo-2-methoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-i-propoxy-carbonyl-ethyl)-phenyl, 2,4-dichloro-5-(2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-allylaminocarbonyl-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-ethoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-cyclopropylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-dimethylaminocarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-ethylsulphonylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-carboxy-ethenyl)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(2-ethylaminocarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(1-ethoxy-carbonylethyl)-phenyl, 2-chloro-4-cyano-5-carboxy-phenyl, 2-fluoro4-chloro-5-(1-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(1-i-propoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-i-butoxy-phenyl, 2-chloro-4-cyano-5-i-butoxy-phenyl, 2-chloro-4-cyano-5-(2-methoxy-ethoxy)-phenyl, 2-fluoro-4-chloro-5-(2-methoxy-ethoxy)-phenyl, 2-fluoro-4-chloro-5-i-butoxy-phenyl, 2-fluoro-4-hydroxy-5-i-propoxy-carbonyl-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxycarbonylmethoxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl, 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1. 
Ar has for example the meanings listed above in Group 1.
Using, for example, 4-fluoro-6-methyl-pyridazin-3-one and 4,5-difluoro-2-methoxy-benzonitrile as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following scheme: 
Using, for example, 4,4,4-trichloro-3-methyl-crotonal dehyde and 2,4-dichloro-5-trifluoromethyl-phenylhydrazine as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following scheme: 
Using, for example, N-(4-bromo-2-fluoro-5-methoxy-carbonyl-phenyl)-hydrazone mucochloric acid as starting material, the course of the reaction in the process (c) according to the invention can be illustrated by the following scheme: 
Using, for example, 2-(2,4-dichloro-phenyl)-4,5,6-trichloro-pyridazin-3-one and nitric acid as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following scheme: 
The formula (II) provides a general definition of the halogenoarenes to be used as starting materials in the process (a) according to the invention for preparing the compounds of the formula (I). In the formula (II), R1, R2 and R3 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R1, R2 and R3; X1 preferably represents fluorine, chlorine or bromine, in particular fluorine.
The starting materials of the formula (II) are known and/or can be prepared by known processes (cf. EP 191181, EP 370332, EP 431373, EP 441004).
The formula (III) provides a general definition of the pyridazinones further to be used as starting materials in the process (a) according to the invention. In the formula (III), R4, R5 and R6 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R4, R5 and R6.
The starting materials of the formula (III) are known and/or can be prepared by known processes (cf. J. Chem. Soc. 1947, 239; Angew. Chem. 77 (1965), 282, Monatsh. Chem. 120 (1989), 329).
The formula (IV) provides a general definition of the arylhydrazines to be used as starting materials in the process (b) according to the invention for preparing the compounds of the formula (I). In the formula (IV), R1, R2 and R3 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R1, R2 and R3.
The starting materials of the formula (IV) are known and/or can be prepared by known processes (cf. EP 370332).
The formula (V) provides a general definition of the xcex2-trihalomethyl-enones further to be used as starting materials in the process (b) according to the invention. In the formula (V), R4, R5 and R 6 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R4, R5 and R6; X2 preferably represents fluorine, chlorine or bromine, in particular chlorine.
The starting materials of the formula (V) are known and/or can be prepared by known processes (cf. DE 2706700).
The formula (VI) provides a general definition of the hydrazonecarboxylic acids to be used as starting materials in the process (c) according to the invention for preparing the compounds of formula (I). In the formula (VI), R1, R2, R3, R4, R5 and R6 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R1, R2, R3, R4, R5 and R6.
The starting materials of the formula (VI) have not been disclosed in the literature; as novel compounds, they form part of the subject matter of the present application.
The novel hydrazonecarboxylic acids of the general formula (VI) are obtained when arylhydrazines of the general formula (IV) 
in which
R1, R2 and R3 are each as defined above
are reacted with xcex2-carboxy-enones of the general formula (VII) 
in which
R4, R5 and R6 are each as defined above,
if appropriate in the presence of a diluent such as, for example, ethanol, and if appropriate in the presence of a reaction auxiliary such as, for example, p-toluene-sulphonic acid, at temperatures between 0xc2x0 C. and 100xc2x0 C. (cf. the Preparation Examples).
The formula (Ia) provides a general definition of the 2,4-disubstituted phenyl-pyridazinones to be used as starting materials in the process (d) according to the invention for preparing the compounds of the formula (I). In the formula (Ia), R1, R2, R4, R5 and R6 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R1, R2, R4, R5 and R6.
The starting materials of the formula (Ia) are known and/or can be prepared by known processes (cf. the processes (a) to (c) according to the invention).
The processes (a), (b), (c) and (d) for preparing the compounds of the formula (I) according to the invention are preferably carried out in the presence of a diluent. Suitable diluents are generally the customary organic solvents. These preferably include aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane (chloroform) or carbon tetrachloride, dialkyl ethers such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether, ethyl t-butyl ether, methyl t-pentyl ether (MTBE), ethyl t-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether or ethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol diethyl ether; dialkyl ketones such as, for example, acetone, butanone (methyl ethyl ketone), methyl i-propyl ketone or methyl i-butyl ketone, nitriles such as, for example, acetonitrile, propionitrile, butyronitrile or benzonitrile; amides such as, for example, N,N-dimethyl-formamide (DMF), N,N-dimethyl-acetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl-phosphoric triamide; esters such as, for example, methyl acetate, ethyl acetate, n- or i-propyl acetate, n-, i- or s-butyl acetate; sulphoxides such as, for example, dimethyl sulphoxide; alkanols such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; their mixtures with water or pure water. In the process (b) according to the invention, acetic acid may also be used advantageously as diluent.
The processes (a) and (b) according to the invention for preparing the compounds of the formula (I) are preferably carried out in the presence of a suitable reaction auxiliary. Suitable reaction auxiliaries are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-propoxide, sodium n-, i-, s- or t-butoxide or potassium n-, i-, s- or t-butoxide, furthermore also basic organic nitrogen compounds such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclo-hexylamine, N,Nxe2x80x94dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2.2.2]-octane (DABCO), 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN), and 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
The process (c) according to the invention for preparing the compounds of the formula (I) is carried out in the presence of a dehydrating agent. Suitable for this purpose are the customary dehydrating agents such as, for example, sulphur acid, methane sulphonic acid, benzene sulphonic acid, p-toluenesulphonic acid acetic anhydride and phosphorus(V) oxide.
The process (d) according to the invention for preparing the compounds of the formula (I) is carried out using a nitrating agent. Suitable for this purpose are the customary nitrating agents such as, for example, nitric acid and mixtures thereof with nitration auxiliaries such as, for example, sulphuric acid.
When carrying out the processes (a), (b), (c) and (d) according to the invention, the reaction temperatures can be varied over a relatively wide range. In general, temperatures of between xe2x88x9220xc2x0 C. and +200xc2x0 C., preferably temperatures of between 0xc2x0 C. and 150xc2x0 C., in particular between 10xc2x0 C. and 120xc2x0 C., are employed.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
In the practice of the processes (a), (b), (c) and (d) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively large excess. The reaction is generally carried out in a suitable diluent, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required. Work-up is carried out according to customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm-killers and, especially, as weed-killers. Weeds, in the broadest sense, are to be understood as meaning all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita. Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for the selective control of dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre- and the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formiers.
If the extender used is water, it is also possible to use for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents include: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkyl-aryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methyl cellulose.
Tackifiers such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be used as such or, in their formulations, as a mixture with known herbicides for the control of weeds, in which case ready-to-use formulations or tank mixes are possible.
Suitable co-components for the mixtures are known herbicides, for example anilides such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacet-anilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as, for example, oryzalin, pendimethalin and trifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet; sulphonylureas such as, for example, amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates such as, for example, butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines such as, for example, atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones such as, for example, hexazinone, metamitron and metribuzin; others such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.